CN113948799A - Hybrid energy lithium-air battery and charging mode thereof - Google Patents
Hybrid energy lithium-air battery and charging mode thereof Download PDFInfo
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Abstract
The invention provides a lithium-air battery, comprising a positive electrode; and the positive electrode is compounded with a photoelectric semiconductor material. The invention combines light energy with the metal-air battery, integrates the photoelectric anode material into the lithium-air battery by utilizing the open battery system of the lithium-air battery, directly converts solar energy into electric energy, and can further reduce the overpotential of the lithium-air battery. The invention comprehensively utilizes the photo-generated electricity property of the semiconductor material to solve the problem of high overpotential of the lithium air battery, integrates the light energy and the electric energy into an energy storage device, optimally combines the solar battery and the lithium air battery, not only has the advantages of the solar battery, but also can solve the problem of high overpotential of the lithium air battery, and integrates the solar battery and the lithium air battery into a battery system, thereby having compact structure, simple manufacturing method and easy subsequent industrial development.
Description
Technical Field
The invention belongs to the technical field of metal-air batteries, relates to a lithium-air battery and a charging mode thereof, and particularly relates to a hybrid energy lithium-air battery and a charging method thereof.
Background
The energy problem is always a key problem for restricting the development and progress of the human society. With the increasing exhaustion of non-renewable energy sources such as fossil energy and the increasing severity of environmental problems, the search for new green and safe energy sources becomes the focus of worldwide attention. Solar energy is considered to be the most green and ideal alternative energy source due to the advantages of environmental friendliness and abundant resources. The current solar energy utilization mode mainly generates heat and electricity, and the intermittency and instability of the solar energy cause the solar energy to need matched energy storage equipment for collecting and storing the energy. Lithium air batteries have received much attention as energy storage devices with the highest theoretical energy density, however, the development of lithium air batteries is restricted by side reactions associated with electrolyte decomposition caused by higher overpotentials.
Therefore, how to prepare a more suitable lithium battery, further improve the performance of the metal-air battery, and reduce the higher overpotential thereof has become one of the focuses of great attention of many leading-edge researchers in the field.
Disclosure of Invention
In view of the above, the present invention provides a lithium air battery and a charging method thereof, and particularly provides a lithium air battery using a hybrid energy of optical energy and electric energy. The lithium-air battery provided by the invention can be charged by utilizing solar energy, and can reduce the high overpotential of the lithium-air battery, so that the light energy and the electric energy are integrated into an energy storage device.
The invention provides a lithium-air battery, comprising a positive electrode;
and the positive electrode is compounded with a photoelectric semiconductor material.
Preferably, the lithium-air battery is a light charging lithium-air battery;
the generated decomposition potential of the lithium oxide is between the conduction band and the valence band of the photoelectric semiconductor material.
Preferably, the optoelectronic semiconductor material comprises TiO2 Doped TiO 22Semiconductor material, C3N4And doping with C3N4One or more of a semiconductor material;
the valence band potential of the photoelectric semiconductor material is greater than the decomposition potential of lithium peroxide;
the material of the positive electrode comprises carbon and/or nickel;
the topography of the positive electrode includes a porous gas diffusion layer.
Preferably, the doped TiO2The semiconductor material comprises TiO doped with one or more of Ru, Au, Pt, Co and Ni2A semiconductor material;
the doping C3N4The semiconductor material comprises C doped with one or more of Ru, Au, Pt, Co and Ni3N4A semiconductor material;
the decomposition potential of the lithium peroxide was 2.96V.
Preferably, the positive electrode includes one or more of carbon paper, carbon cloth, and nickel foam;
the compounding manner comprises one or more of growing, depositing, coating, spraying and dipping;
the photoelectric semiconductor material loading capacity is (0.1-2) mg/cm2。
Preferably, the lithium-air battery is a hybrid energy air battery;
the lithium air battery further includes one or more of an electrolyte, a separator, a negative electrode, and a current collector;
the electrolyte includes one or more of a liquid electrolyte, a gel electrolyte, and a solid electrolyte.
Preferably, the separator comprises a glass fiber film and/or a PP film;
the negative electrode includes a lithium negative electrode;
the current collector includes a nickel foam and/or a stainless steel mesh.
Preferably, the liquid electrolyte includes a lithium salt electrolyte and an organic solvent;
the lithium salt electrolyte comprises one or more of lithium trifluoromethanesulfonate, lithium perchlorate and lithium bistrifluoromethylsulfonimide;
the organic solvent comprises one or more of tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol dimethyl ether and dimethyl sulfoxide.
The invention also provides a charging mode of the lithium-air battery, and the lithium-air battery is charged under the illumination condition to obtain a charged lithium-air battery;
and/or
Under the condition of no illumination, an external power supply is adopted for charging to obtain a charged lithium air battery;
the lithium air battery is a light charging lithium air battery.
Preferably, the wavelength band of the illumination comprises a visible light wavelength band and/or an ultraviolet light wavelength band;
the overpotential of the charged lithium air battery obtained by charging under the illumination condition is smaller than the overpotential of the charged lithium air battery obtained by charging through the external power supply;
compared with the overpotential of the charged lithium air battery obtained by charging the external power supply under the illumination condition, the overpotential of the charged lithium air battery obtained by charging the external power supply is reduced by 10% -30%.
The invention provides a lithium-air battery, comprising a positive electrode; and the positive electrode is compounded with a photoelectric semiconductor material. Compared with the prior art, the invention aims at the problems that the development of the existing metal-air battery is restricted by side reactions related to electrolyte decomposition caused by higher overpotential and the like. The invention creatively combines light energy with the metal-air battery, integrates a photoelectric anode material into the lithium-air battery by utilizing an open battery system of the lithium-air battery, directly converts solar energy into electric energy, and can further reduce the overpotential of the lithium-air battery, thereby obtaining the lithium-air battery with a specific structure and composition. The invention comprehensively utilizes the photo-generated electricity property of the semiconductor material to solve the problem of high overpotential of the lithium air battery, and integrates the photo-generated electricity and the electric energy into an energy storage device.
The invention arranges a specific photoelectric semiconductor material in the lithium air battery, under the illumination condition, the semiconductor material absorbs sunlight to realize the separation of photo-generated electrons and holes, and the photo-generated electrons are transmitted to the negative electrode through an external circuit during charging and are combined with lithium ions to deposit on the negative electrode. The photogenerated holes oxidize the discharge product lithium peroxide to decompose and release oxygen. Thereby completing the conversion of light energy to chemical energy. In addition, when no light exists, the charging process is the same as that of a common battery, and lithium peroxide is decomposed by an external power supply, so that the conversion from electric energy to chemical energy is realized. The light charging lithium-air battery can directly utilize sunlight to charge the battery in an auxiliary mode, solar energy is directly converted into electric energy, reaction overpotential of the lithium-air battery is reduced, and conversion from the solar energy to the electric energy in the battery is achieved. The solar battery and the lithium air battery are optimally combined, the solar battery has the advantages of the solar battery, the problem of high overpotential of the lithium air battery can be solved, and the solar battery and the lithium air battery are integrated into a battery system, so that the solar battery and the lithium air battery are compact in structure, simple in manufacturing method and easy for subsequent industrial development.
The experimental result shows that under the condition of simulating solar illumination, the charging potential of the lithium air battery using the semiconductor photoelectric anode material is obviously reduced, the charging cut-off potential is reduced to about 4V from the initial 4.5V, the conversion and storage from solar energy to electric energy are realized, and a foundation is laid for exploring and developing an integrated solar energy storage battery.
Drawings
FIG. 1 is a schematic diagram of the structure of a photo-rechargeable lithium-air battery according to the present invention;
FIG. 2 shows spray coating C prepared in example 13N4The first charge-discharge curve of the photoelectrode in the absence of illumination;
FIG. 3 shows in-situ growth C prepared in example 23N4The first charge-discharge curve of the photoelectrode in the absence of illumination;
FIG. 4 shows in-situ grown TiO prepared in example 32The first charge-discharge curve of the photoelectrode in the absence of illumination;
FIG. 5 shows in-situ grown defective TiO prepared in example 42-xFirst charge-discharge curve of photoelectrode under the condition of no light.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs analytically pure or purity conventional in the field of metal-air batteries.
The invention provides a lithium-air battery, which comprises a positive electrode;
and the positive electrode is compounded with a photoelectric semiconductor material.
In the present invention, the lithium-air battery preferably includes a lithium oxygen battery. That is, in the present invention, the lithium-air battery can be equivalently regarded as a lithium oxygen battery.
In the present invention, the material of the positive electrode preferably includes carbon and/or nickel, and more preferably includes carbon or nickel.
In the present invention, the topography of the positive electrode preferably includes a porous gas diffusion layer.
In the present invention, the positive electrode preferably includes one or more of carbon paper, carbon cloth, and nickel foam, and more preferably, carbon paper, carbon cloth, or nickel foam.
In the present invention, the compounding means preferably includes one or more of growth, deposition, coating, spraying and dipping, and more preferably, a plurality of growth, deposition, coating, spraying and dipping.
In the present invention, the photoelectric semiconductor material is preferably a photoelectric semiconductor material stably existing in a lithium air battery system.
In the present invention, the optoelectronic semiconductor material preferably comprises TiO2Doped TiO 22Semiconductor material, C3N4And doping with C3N4One or more of the semiconductor materials, more preferably TiO2Doped TiO 22Semiconductor material, C3N4Or doped with C3N4A semiconductor material.
In the present invention, the doped TiO2The semiconductor material preferably comprises one or more of Ru, Au, Pt, Co and NiDoped TiO2Semiconductor material, more preferably TiO doped with Ru, Au, Pt, Co or Ni2A semiconductor material.
In the present invention, the doping C3N4The semiconductor material preferably comprises C doped with one or more of Ru, Au, Pt, Co and Ni3N4Semiconductor material, more preferably C doped with Ru, Au, Pt, Co or Ni3N4A semiconductor material.
In the present invention, the generation decomposition potential of the lithium oxide is preferably between the conduction band and the valence band of the photoelectric semiconductor material.
In the present invention, the valence band potential of the photoelectric semiconductor material is preferably greater than the decomposition potential of lithium peroxide.
In the present invention, the decomposition potential of the lithium peroxide is preferably 2.96V.
In the invention, the loading capacity of the photoelectric semiconductor material is preferably (0.1-2) mg/cm2More preferably (0.4 to 1.6) mg/cm2More preferably (0.8 to 1.2) mg/cm2。
In the present invention, the lithium-air battery is preferably a photo-rechargeable lithium-air battery.
In the present invention, the lithium-air battery is preferably a hybrid energy air battery.
In the present invention, the lithium air battery preferably includes one or more of an electrolyte, a separator, a negative electrode, and a current collector, and more preferably, the electrolyte, the separator, the negative electrode, and the current collector.
In the present invention, the electrolyte is preferably an electrolyte that stably exists under light irradiation.
In the present invention, the electrolyte preferably includes one or more of a liquid electrolyte, a gel electrolyte, and a solid electrolyte, and more preferably a liquid electrolyte, a gel electrolyte, or a solid electrolyte.
In the present invention, the liquid electrolyte is preferably a liquid electrolyte that is stable in the presence of light and has solubility to oxygen.
In the present invention, the liquid electrolyte preferably includes a lithium salt electrolyte and an organic solvent.
In the present invention, the lithium salt electrolyte preferably includes one or more of lithium trifluoromethanesulfonate, lithium perchlorate and lithium bistrifluoromethylsulfonyl imide, and more preferably lithium trifluoromethanesulfonate, lithium perchlorate or lithium bistrifluoromethylsulfonyl imide.
In the present invention, the organic solvent preferably includes one or more of tetraglyme, triglyme, diglyme and dimethyl sulfoxide, and more preferably tetraglyme, triglyme, diglyme or dimethyl sulfoxide.
In the present invention, the separator preferably includes a glass fiber film and/or a PP film, and more preferably a glass fiber film or a PP film.
In the present invention, the negative electrode preferably includes a lithium negative electrode.
In the present invention, the current collector preferably includes a nickel foam and/or a stainless steel mesh, more preferably a nickel foam or a stainless steel mesh.
The invention integrates and refines the whole technical scheme, better ensures the specific composition and structure of the lithium-air battery, improves the comprehensive performance of the lithium-air battery, and further reduces the charging overpotential, and the lithium-air battery can be specifically of the following structure and composition:
the invention provides a light charging lithium-air battery, which comprises a gas diffusion layer (a conventional lithium-air battery anode material), a photoelectric semiconductor anode material, an electrolyte, a diaphragm, a negative electrode and a current collector. The lithium air battery directly utilizes sunlight to charge the battery in an auxiliary manner under the action of the semiconductor anode, so that the direct conversion of solar energy into electric energy is realized, and the reaction overpotential of the lithium air battery is reduced. The conversion of solar energy into electric energy inside the cell is realized.
In particular, the optoelectronic semiconductor material preferably comprises TiO2、C3N4And derived semiconductor materials thereof. These optoelectronic semiconductor materials have a decomposition potential for the generation of lithium peroxide between the conduction and valence bands of the semiconductor material.
Specifically, the positive semiconductor material is grown in situ or sprayed on a gas diffusion layer such as carbon paper, carbon cloth, foamed nickel and the like.
Specifically, the electrolyte is an electrolyte commonly used for a lithium air battery, and comprises a liquid electrolyte or a gel and a solid electrolyte. Wherein the liquid electrolyte comprises a lithium salt electrolyte and an organic solvent;
the lithium salt electrolyte comprises one or more of lithium trifluoromethanesulfonate, lithium perchlorate and lithium bistrifluoromethylsulfonimide;
the organic solvent comprises one or more of tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether and dimethyl sulfoxide.
Specifically, the diaphragm is a glass fiber film or a PP film, and the negative electrode is a lithium negative electrode.
The invention provides a light charging lithium air battery, which comprises C3N4、TiO2And a semiconductor anode material derived from the same, wherein the anode material is prepared by an in-situ growth method for better contact between the electrode material and an anode carrier; under illumination, after the anode of the load semiconductor material absorbs light, generated electrons and holes are respectively transferred to the cathode through an external circuit, the decomposition of a discharge product is promoted, the charge potential is reduced, and the simultaneous storage of electric energy and solar energy is realized.
The photoelectric anode in the invention comprises TiO2、C3N4And derived semiconductor materials thereof. These optoelectronic semiconductor materials need to be stable in lithium air battery systems and have the generation and decomposition potential of lithium peroxide between the conduction and valence bands of the semiconductor material. The anode semiconductor material is grown in situ or sprayed on a gas diffusion layer such as carbon paper, carbon cloth, foamed nickel and the like.
The electrolyte in the invention is the electrolyte commonly used by the lithium air battery, and comprises liquid electrolyte or gel and solid electrolyte. The electrolyte needs to be stable in light and have a certain solubility for oxygen. The diaphragm is a glass fiber film or a PP film, and the negative electrode is a lithium negative electrode. The current collector is made of materials with good conductivity and chemical stability, such as foamed nickel, stainless steel mesh and the like.
The invention can directly utilize solar energy to charge the battery through the light response of the specific semiconductor photoelectric anode, obviously reduce the overpotential of the battery and realize the conversion of the solar energy, chemical energy and electric energy. The invention has the advantages that the solar cell and the lithium air cell are combined, the photoelectric conversion can be realized by utilizing solar energy, the overpotential of the lithium air cell can be reduced, and the electrolyte decomposition and side reaction caused by high potential can be reduced. The hybrid energy air battery has the advantages of environmental friendliness and energy conservation.
Referring to fig. 1, fig. 1 is a schematic diagram of a structure of a photo-rechargeable lithium-air battery according to the present invention. Where 1 is a lithium negative electrode, 2 is a separator, 3 is a positive electrode support, 4 is a current collector, 5 is a negative electrode can, and 6 is a positive electrode can.
The invention provides a charging mode of a lithium-air battery, which is characterized in that the lithium-air battery is charged under the condition of illumination to obtain a charged lithium-air battery;
and/or
Under the condition of no illumination, an external power supply is adopted for charging to obtain a charged lithium air battery;
the lithium air battery is a light charging lithium air battery.
In the present invention, the charging method is a charging method.
In the present invention, the wavelength band of the illumination preferably includes a visible light wavelength band and/or an ultraviolet light wavelength band, and more preferably, the visible light wavelength band or the ultraviolet light wavelength band. Specifically, sunlight can be used.
In the present invention, the overpotential of the charged lithium-air battery charged under the illumination condition is preferably smaller than the overpotential of the charged lithium-air battery charged by the external power supply.
In the present invention, the overpotential of the charged lithium-air battery charged under the illumination condition is preferably reduced by 10% to 30%, more preferably 12% to 28%, more preferably 15% to 25%, and more preferably 18% to 23% as compared with the overpotential of the charged lithium-air battery charged by the external power source. In the present invention, different semiconductors have slightly different ability to reduce overpotential.
The lithium air battery provided by the invention can be charged under the condition of illumination, can be charged by using an external power supply under the condition of no illumination, can conflict by using similar light sources such as sunlight under the condition of illumination, and can be charged by using light energy and electric energy at the same time.
The invention integrates and refines the whole technical scheme, better ensures the specific composition and structure of the lithium-air battery, improves the comprehensive performance of the lithium-air battery, and further reduces the charging overpotential, and the charging mode (working principle) of the light charging lithium-air battery can specifically comprise the following steps:
the cell is normally assembled, a xenon lamp light source (simulating sunlight) is introduced to the positive electrode side, and the photoelectric semiconductor material generates electricity, so that the charging overpotential is reduced.
When the battery is charged and under the illumination condition, the semiconductor material absorbs light energy, so that internal electrons are transited to an excited state, the electrons in the excited state are led into the negative electrode through an external circuit and are combined with lithium ions to be deposited on the negative electrode, the photoproduced holes are highly oxidized, lithium peroxide is decomposed to release oxygen due to the high oxidizing property, the lithium ions are combined with the electrons transmitted by the external circuit under the driving of an external electric field to be deposited on the lithium negative electrode, and the conversion from the light energy to the electric energy to the chemical energy is completed.
The invention reduces the charging potential due to the introduction of light energy, and increases the utilization efficiency of energy. And the solar cell and the lithium air cell are optimally combined, so that the solar cell has the advantages of the solar cell, the problem of high overpotential of the lithium air cell can be solved, and the solar cell and the lithium air cell are integrated into a cell system, so that the structure is compact, and the manufacturing method is simple.
The invention provides a hybrid energy lithium-air battery and a charging method thereof, in particular to a light energy and electric energy hybrid energy lithium-air battery and a charging method utilizing solar energy. The invention combines light energy and a metal air battery, integrates a photoelectric anode material into the lithium air battery by utilizing an open battery system of the lithium air battery, directly converts solar energy into electric energy, and can further reduce the overpotential of the lithium air battery, thereby obtaining the lithium air battery with a specific structure and composition. The invention comprehensively utilizes the photo-generated electricity property of the semiconductor material to solve the problem of high overpotential of the lithium air battery, and integrates the photo-generated electricity and the electric energy into an energy storage device.
The invention arranges a specific photoelectric semiconductor material in the lithium air battery, under the illumination condition, the semiconductor material absorbs sunlight to realize the separation of photo-generated electrons and holes, and the photo-generated electrons are transmitted to the negative electrode through an external circuit during charging and are combined with lithium ions to deposit on the negative electrode. The photogenerated holes oxidize the discharge product lithium peroxide to decompose and release oxygen. Thereby completing the conversion of light energy to chemical energy. In addition, when no light exists, the charging process is the same as that of a common battery, and lithium peroxide is decomposed by an external power supply, so that the conversion from electric energy to chemical energy is realized. The light charging lithium-air battery can directly utilize sunlight to charge the battery in an auxiliary mode, solar energy is directly converted into electric energy, reaction overpotential of the lithium-air battery is reduced, and conversion from the solar energy to the electric energy in the battery is achieved. The solar battery and the lithium air battery are optimally combined, the solar battery has the advantages of the solar battery, the problem of high overpotential of the lithium air battery can be solved, and the solar battery and the lithium air battery are integrated into a battery system, so that the solar battery and the lithium air battery are compact in structure, simple in manufacturing method and easy for subsequent industrial development.
The experimental result shows that under the condition of simulating solar illumination, the charging potential of the lithium air battery using the semiconductor photoelectric anode material is obviously reduced, the charging cut-off potential is reduced to about 4V from the initial 4.5V, the conversion and storage from solar energy to electric energy are realized, and a foundation is laid for exploring and developing an integrated solar energy storage battery.
For further illustration of the present invention, a lithium air battery and a charging method thereof provided by the present invention are described in detail with reference to the following examples, but it should be understood that the examples are carried out on the premise of the technical solution of the present invention, and the detailed embodiments and specific operation procedures are given only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
(1) Preparing a semiconductor material: placing melamine or urea in a corundum crucible, calcining for 4 hours in a muffle furnace at 550 ℃ to generate yellow solid C3N4(ii) a After cooling to room temperature, washing with absolute ethyl alcohol for three times, drying to constant weight, crushing, and fully grinding for later use. Preparing a photoelectric anode: mixing the powder C3N4Fully and uniformly grinding the mixture in NMP solution to be pasty, spraying the mixture on a carbon paper air diffusion layer, placing the carbon paper air diffusion layer in a constant-temperature oven, drying the carbon paper air diffusion layer to constant weight, and cutting the carbon paper air diffusion layer into pieces to obtain the photoelectric semiconductor anode.
(2) The electrolyte consists of 1M TEGDME solution of LiTFSI, a negative electrode is a lithium sheet, a diaphragm is a glass fiber membrane, and a current collector is foamed nickel.
(3) And assembling the semiconductor anode, the diaphragm and the current collector together according to the structure, injecting 100uL of electrode liquid, and packaging the connecting wire to form the light charging lithium-air battery.
(4) Lithium air battery now 200mA g-1Was discharged for 5 hours and then photo-charged for 5 hours at a light intensity of 100 milliwatts per square centimeter, and the light source was turned off.
The performance of the hybrid energy lithium-air battery prepared in example 1 of the invention was tested, and the charging and discharging curves with and without light were compared.
Referring to FIG. 2, FIG. 2 shows spray coating C prepared in example 13N4First charge-discharge curve of photoelectrode under the condition of no light.
The detection conditions are as follows: at 0.1mA/cm-1Discharged for 5h at current density and then charged again for 5h without light.
As can be seen from fig. 2, after charging for 5h in the absence of light, the voltage reaches 4.54V, and the overpotential is 4.54-2.96V — 1.58V; under the condition of illumination, the charging voltage is reduced to 4.24V, the overpotential is reduced by 0.3V, and the reduction amplitude is 18.9%.
Example 2
Preparing a semiconductor material: the melamine is ground into powder, dissolved in water to form paste and sprayed on the carbon paper flow collection bodyCalcining the mixture in a corundum crucible in a muffle furnace at 550 ℃ for 4 hours to generate yellow solid C3N4(ii) a After cooling to room temperature, washing with absolute ethyl alcohol for three times, and drying to constant weight. Thus preparing C3N4And the photoelectric anode grows on the carbon-based air diffusion layer in situ.
(2) The electrolyte consists of 1M TEGDME solution of LiTFSI, a negative electrode is a lithium sheet, a diaphragm is a glass fiber membrane, and a current collector is foamed nickel.
(3) And assembling the semiconductor anode, the diaphragm and the current collector together according to the structure, injecting 100uL of electrode liquid, and packaging the connecting wire to form the light charging lithium-air battery.
(4) Lithium air battery now 100mA g-1Was discharged for 5 hours and then photo-charged for 5 hours at a light intensity of 100 milliwatts per square centimeter, and the light source was turned off.
The performance of the hybrid energy lithium-air battery prepared in example 2 of the invention was tested and compared with the charging and discharging curves with or without light.
Referring to FIG. 3, FIG. 3 shows in-situ growth C prepared in example 23N4First charge-discharge curve of photoelectrode under the condition of no light.
The detection conditions are as follows: at 0.1mA/cm-1Discharged for 5h at current density and then charged again for 5h without light.
As can be seen from fig. 3, after charging for 5h in the absence of light, the voltage reached 4.62V, and the overpotential was 4.62-2.96V — 1.66V; under the condition of illumination, the charging voltage is reduced to 4.18V, the overpotential is 1.22V, the reduction is 0.44V, and the reduction amplitude is 26.50%.
Example 3
(1) Preparing a semiconductor material: a) firstly, ultrasonically cleaning air diffusion layers such as carbon paper and the like for three times by using acetone and pure water respectively and drying the air diffusion layers in vacuum at the temperature of 60 ℃; b) putting the cleaned carbon paper in butyl carbonate isopropanol solution, cleaning with ethanol after full immersion, drying at 80 ℃ to constant weight, annealing at 500 ℃ for 1h to form TiO on the carbon paper2Seed crystals; c) the carbon paper containing the seed crystal is dipped into the isopropanol solution containing the butyl carbonate again and added with a proper amount of hydrochloric acid solution to be stirredAfter being uniformly mixed, the mixture is moved into a high-pressure reaction kettle and reacts for 10 hours at the temperature of 150 ℃; d) after the reaction is completed, taking out the carbon paper, washing the carbon paper for 3 times by using pure water, and drying the carbon paper in a vacuum box at 60 ℃ to obtain the loaded TiO2The carbon paper photoelectric anode.
(2) The electrolyte consists of 1M TEGDME solution of LiTFSI, a negative electrode is a lithium sheet, a diaphragm is a glass fiber membrane, and a current collector is foamed nickel.
(3) And assembling the semiconductor anode, the diaphragm and the current collector together according to the structure, injecting 100uL of electrode liquid, and packaging the connecting wire to form the light charging lithium-air battery.
(4) Lithium air battery now 100mA g-1Was discharged for 5 hours and then photo-charged for 5 hours at a light intensity of 100 milliwatts per square centimeter, and the light source was turned off.
The performance of the hybrid energy lithium-air battery prepared in example 3 of the invention was tested and compared with the charging and discharging curves with or without light.
Referring to FIG. 4, FIG. 4 shows in-situ grown TiO prepared in example 32First charge-discharge curve of photoelectrode under the condition of no light.
The detection conditions are as follows: at 0.1mA/cm-1Discharged for 5h at current density and then charged again for 5h without light.
As can be seen from fig. 4, after charging for 5h in the absence of light, the voltage reached 4.57V, and the overpotential was 4.57-2.96V — 1.61V; under the condition of illumination, the charging voltage is reduced to 4.11V, the overpotential is 1.15V, the reduction is 0.46V, and the reduction amplitude is 28.57%.
Example 4
(1) Preparing a semiconductor material: a) firstly, ultrasonically cleaning air diffusion layers such as carbon paper and the like for three times by using acetone and pure water respectively and drying the air diffusion layers in vacuum at the temperature of 60 ℃; b) putting the cleaned carbon paper in butyl carbonate isopropanol solution, cleaning with ethanol after full immersion, drying at 80 ℃ to constant weight, annealing at 500 ℃ for 1h to form TiO on the carbon paper2Seed crystals; c) soaking the carbon paper containing the seed crystal into an isopropanol solution containing butyl carbonate again, adding a proper amount of hydrochloric acid solution, stirring uniformly, moving into a high-pressure reaction kettle, and reacting for 10 hours at 150 ℃; d) taking out the carbon paper after the reaction is completed, and using pure waterWashing for 3 times, and drying at 60 deg.C in vacuum oven to obtain supported TiO2The carbon paper photoelectric anode. In order to improve the photoelectrocatalytic activity, the material is bombarded by argon plasma to prepare TiO rich in defects2-X。
(2) The electrolyte consists of 1M TEGDME solution of LiTFSI, a negative electrode is a lithium sheet, a diaphragm is a glass fiber membrane, and a current collector is foamed nickel.
(3) And assembling the semiconductor anode, the diaphragm and the current collector together according to the structure, injecting 100uL of electrode liquid, and packaging the connecting wire to form the light charging lithium-air battery.
(4) Lithium air battery now 100mA g-1Was discharged for 5 hours and then photo-charged for 5 hours at a light intensity of 100 milliwatts per square centimeter, and the light source was turned off.
The performance of the hybrid energy lithium-air battery prepared in example 4 of the invention was tested and compared with the charging and discharging curves with or without light.
Referring to FIG. 5, FIG. 5 shows the in-situ grown defective TiO prepared in example 42-xFirst charge-discharge curve of photoelectrode under the condition of no light.
The detection conditions are as follows: at 0.1mA/cm-1Discharged for 5h at current density and then charged again for 5h without light.
As can be seen from fig. 5, after charging for 5h in the absence of light, the voltage reaches 4.58V, and the overpotential is 4.58-2.96V — 1.62V; under the condition of illumination, the charging voltage is reduced to 4.20V, the overpotential is 1.24V, the reduction is 0.38V, and the reduction amplitude is 23.45%.
The foregoing detailed description of a hybrid energy lithium air battery and method of charging the same provided by the present invention has been presented using specific examples to illustrate the principles and implementations of the invention, and the above description of the examples is provided only to facilitate the understanding of the method and its core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A lithium-air battery, comprising a positive electrode;
and the positive electrode is compounded with a photoelectric semiconductor material.
2. The lithium-air battery of claim 1, wherein the lithium-air battery is a photo-charged lithium-air battery;
the generated decomposition potential of the lithium oxide is between the conduction band and the valence band of the photoelectric semiconductor material.
3. The lithium-air battery of claim 1, wherein the optoelectronic semiconductor material comprises TiO2Doped TiO 22Semiconductor material, C3N4And doping with C3N4One or more of a semiconductor material;
the valence band potential of the photoelectric semiconductor material is greater than the decomposition potential of lithium peroxide;
the material of the positive electrode comprises carbon and/or nickel;
the topography of the positive electrode includes a porous gas diffusion layer.
4. The lithium-air battery of claim 3, wherein the doped TiO2The semiconductor material comprises TiO doped with one or more of Ru, Au, Pt, Co and Ni2A semiconductor material;
the doping C3N4Semiconductor materialThe material comprises C doped with one or more of Ru, Au, Pt, Co and Ni3N4A semiconductor material;
the decomposition potential of the lithium peroxide was 2.96V.
5. The lithium air battery of claim 1, wherein the positive electrode comprises one or more of carbon paper, carbon cloth, and nickel foam;
the compounding manner comprises one or more of growing, depositing, coating, spraying and dipping;
the photoelectric semiconductor material loading capacity is (0.1-2) mg/cm2。
6. The lithium-air battery according to claim 1, wherein the lithium-air battery is a hybrid energy air battery;
the lithium air battery further includes one or more of an electrolyte, a separator, a negative electrode, and a current collector;
the electrolyte includes one or more of a liquid electrolyte, a gel electrolyte, and a solid electrolyte.
7. The lithium-air battery according to claim 6, wherein the separator comprises a fiberglass film and/or a PP film;
the negative electrode includes a lithium negative electrode;
the current collector includes a nickel foam and/or a stainless steel mesh.
8. The lithium-air battery of claim 6, wherein the liquid electrolyte comprises a lithium salt electrolyte and an organic solvent;
the lithium salt electrolyte comprises one or more of lithium trifluoromethanesulfonate, lithium perchlorate and lithium bistrifluoromethylsulfonimide;
the organic solvent comprises one or more of tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol dimethyl ether and dimethyl sulfoxide.
9. A charging mode of a lithium-air battery is characterized in that the lithium-air battery is charged under the condition of illumination to obtain a charged lithium-air battery;
and/or
Under the condition of no illumination, an external power supply is adopted for charging to obtain a charged lithium air battery;
the lithium air battery is a light charging lithium air battery.
10. The charging method according to claim 9, wherein the illumination wavelength band comprises a visible light wavelength band and/or an ultraviolet light wavelength band;
the overpotential of the charged lithium air battery obtained by charging under the illumination condition is smaller than the overpotential of the charged lithium air battery obtained by charging through the external power supply;
compared with the overpotential of the charged lithium air battery obtained by charging the external power supply under the illumination condition, the overpotential of the charged lithium air battery obtained by charging the external power supply is reduced by 10% -30%.
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